WO2006057046A1 - 固体核磁気共鳴装置用試料管 - Google Patents

固体核磁気共鳴装置用試料管 Download PDF

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Publication number
WO2006057046A1
WO2006057046A1 PCT/JP2004/017603 JP2004017603W WO2006057046A1 WO 2006057046 A1 WO2006057046 A1 WO 2006057046A1 JP 2004017603 W JP2004017603 W JP 2004017603W WO 2006057046 A1 WO2006057046 A1 WO 2006057046A1
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WO
WIPO (PCT)
Prior art keywords
sample
tube
sample tube
solid
magnetic resonance
Prior art date
Application number
PCT/JP2004/017603
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Kazuo Yamauchi
Tetsuo Asakura
Original Assignee
National University Corporation Tokyo University Of Agriculture And Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National University Corporation Tokyo University Of Agriculture And Technology filed Critical National University Corporation Tokyo University Of Agriculture And Technology
Priority to PCT/JP2004/017603 priority Critical patent/WO2006057046A1/ja
Priority to DE200511002951 priority patent/DE112005002951T9/de
Priority to US11/791,543 priority patent/US7482810B2/en
Priority to JP2006546621A priority patent/JPWO2006057082A1/ja
Priority to PCT/JP2005/007303 priority patent/WO2006057082A1/ja
Publication of WO2006057046A1 publication Critical patent/WO2006057046A1/ja

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/30—Sample handling arrangements, e.g. sample cells, spinning mechanisms
    • G01R33/307—Sample handling arrangements, e.g. sample cells, spinning mechanisms specially adapted for moving the sample relative to the MR system, e.g. spinning mechanisms, flow cells or means for positioning the sample inside a spectrometer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
    • G01R33/28—Details of apparatus provided for in groups G01R33/44 - G01R33/64
    • G01R33/30—Sample handling arrangements, e.g. sample cells, spinning mechanisms
    • G01R33/302—Miniaturized sample handling arrangements for sampling small quantities, e.g. flow-through microfluidic NMR chips

Definitions

  • the present invention relates to a sample tube for a solid-state nuclear magnetic resonance (solid-state NMR) device, and more particularly to a sample tube effective for high-resolution solid-state NMR of trace substances.
  • solid-state NMR solid-state nuclear magnetic resonance
  • Non-Patent Document 1 Lowe, Phys. Rev. Lett. 2, 285, (1959)
  • Non-Patent Document 2 Andrew, Nature, 183, 1802 (1959)
  • the sample is filled in a sample tube made of ceramic or a polymer material of about several millimeters to 1 centimeter, and this is put in the housing. It is inserted into the arranged coil, and the sample tube housing force is also blown by high-pressure air or gas such as nitrogen to float the sample tube in the air, and at the end or center of the sample tube, it is a turbine shape called a spinner.
  • the sample tube is rotated at a high speed in the coil by feeding high-pressure air into the wings (for example, Patent Documents 1 and 2). Radio wave irradiation and detection are performed by the solenoid type coil arranged around the cylindrical sample tube.
  • Patent Document 1 Japanese Patent Laid-Open No. 55-163447
  • Patent Document 2 JP-A-58-154645
  • a first object of the present invention is to provide a sample tube suitable for measurement of a very small amount of a solid sample by nuclear magnetic resonance (solid state NMR).
  • the second object of the present invention is to provide a sample tube suitable for solid-state nuclear magnetic resonance (solid-state NMR) measurement, in which a small amount of a solid sample can be placed close to a radio-frequency irradiation 'detection coil. It is to provide.
  • the above objects of the present invention are to provide a rotating sample tube for a solid sample used for a probe of a nuclear magnetic resonance apparatus, wherein the sample tube is narrowed at an intermediate portion filled with a solid sample,
  • a sample tube for a solid-state nuclear magnetic resonance apparatus characterized by having a spinner that is removably inserted and fixed at least at one end thereof.
  • the constricted middle portion is a thin tube of uniform thickness.
  • the radio wave is irradiated around the constricted intermediate portion to radiate the sample with radio waves and obtain a signal from the sample. ⁇ It is preferable to place the detection coil close to the sample.
  • the inner diameter of the coil is equal to or smaller than the outer diameters at both ends of the sample tube.
  • the sample tube has an intermediate portion filled with a solid sample, It is preferable that it is formed so as to be split into two parts so that it can be inserted into the radio wave irradiation / detection coil later. Further, it is preferable that the sample tube has removable spinners at both ends thereof, and the outer diameter of the narrowed intermediate portion is preferably 1Z3 or less of the outer diameter of both end portions of the sample tube.
  • FIG. 1 is a cross-sectional view showing an example of a sample tube of the present invention.
  • the sample tube of the present invention may be basically the same as a conventional sample tube except that the central portion is thin. That is, the material is ceramics or plastics as in the past, and a spinner is detachably fixed to at least one end of the sample tube.
  • the sample tube of the present invention will be described based on examples.
  • FIG. 1 is a representative example of the sample tube of the present invention.
  • 10 is a sample tube
  • 1 is a narrow central tube
  • 2 is a non-capillary tube having a normal thickness
  • 3 is a spinner with wings
  • 4 is for radio wave irradiation and detection.
  • the solenoid coil which is a typical example of a coil is represented.
  • the force between the narrow tube portion 1 and the non-capillary tube portion 2 is not necessarily tapered, but may be a vertical surface, for example.
  • the diameter of the thin tube portion 1 is preferably 1Z3 or less of the tube diameter of the non-thin tube portion, and particularly preferably 1 mm or less.
  • the turbine part of the spinner Uses a larger one than the outer diameter of the non-thin tube for stable rotation.
  • the material of the sample tube of the present invention is a force that can be appropriately selected from among those used in solid state NMR sample tubes.
  • a plastic is used for a spinner.
  • the thin tube portion 1 and the non-thin tube portion 2 may be integrally formed as shown in FIG. 1, but at least one of the non-thin tube portions 2 may be formed so as to be separable from the thin tube portion 1.
  • the narrow tube portion can be easily inserted into the solenoid coil 4 having a smaller inner diameter than the non-thin tube portion 2 later.
  • the solenoid coil is arranged in advance so as to be close to the thin tube part, and then the whole is installed in the probe, and the terminal of the solenoid coil is connected to the terminal in the probe. Since it needs to be combined, it becomes complicated.
  • the thin tube portion 1 is, for example, placed at the center of the non-thin tube portion 2 which can be screwed and screwed together.
  • a coupling means may be provided in which a hole for insertion can be provided and an elastic member is disposed therein.
  • the non-thin tube portion 2 and the thin tube portion 1 at both ends can be manufactured separately, and each can be integrally assembled using the two coupling members.
  • a glass capillary filled with a sample can be used and discarded as the thin tube portion, so that it is not only inexpensive but also easy to use.
  • the narrow tube portion can be a closed tube with both ends closed, it is particularly suitable for measurement of a sample that does not like oxygen.
  • the whole of the sample tube that can be actually measured by integrating the coupling member, the non-capillary tube portion, and the spinner to be integrated with only the capillary portion It is included in the definition of the sample tube of the present invention.
  • the spinner is inserted into at least one end of the non-narrow tube portion 2 in the same manner as in the conventional method, for example, a plastic one.
  • a spinner may be provided for each of the two non-capillary sections.
  • the sample tube is rotated by a known method, for example, by flowing air, nitrogen gas or the like so as to rotate the spinner.
  • the sample tube is floated inside by flowing a gas between the non-thin tube portion of the sample tube and its receiving portion. Rotate with
  • Non-Patent Document 3 Yamauchi et al., J. Magn. Reson, 167, 87 (2004)
  • Non-Patent Document 4 The mechanism for efficiently radiating radio waves to obtain NMR signals has been studied by NMR borts and Richards, and the methods for obtaining theoretically obtained signal strength and noise strength are as follows. It is shown (Non-Patent Document 4).
  • B Zi is the magnetic field generated per unit current
  • VS is the sample quantity
  • N is the number of spins per unit sample quantity
  • ⁇ is the nuclear gyromagnetic ratio
  • I is the number of spins ⁇ is the Larmor frequency
  • ⁇ is the temperature
  • H and kB are Planck constant and Boltzmann constant, respectively.
  • Non-Patent Document 4 J. Magn. Reson. 24 71 (1976)
  • the noise component is represented by a noise factor (F) of the spectrometer, a resistance value (Rnoise) of the coil, and an observation width ( ⁇ f).
  • F noise factor
  • Rnoise resistance value
  • ⁇ f observation width
  • ⁇ is the distance from the coil center
  • ⁇ is the magnetic permeability in vacuum
  • ⁇ is the number of turns of the coil
  • R and 1 are the coil diameter and length, respectively.
  • the sensitivity is increased by reducing the coil, and further increasing the number of turns in the case of a solenoid coil.
  • the reason why the solenoid coil is used in the present invention is to increase the uniformity of B to be generated by using the above method, as is often used in solid-state NMR.
  • the signal intensity per single nucleus increases compared to the current one, and the efficiency is improved.
  • it is very effective to make the coil small and place the sample very close (C in the figure). If the rotating turbine part (non-capillary part) is thicker than the sample part (capillary part) and about several millimeters, the rotation error of the sample itself can be reduced to several hertz.
  • sample tube of the present invention is used in NMR, it is necessary not only for solids but also for systems that require stable rotation in systems that require radio wave irradiation and rotation, such as gels, liquid crystals, and solutions. Even a very small amount of sample can be handled.

Landscapes

  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Investigating Or Analyzing Materials By The Use Of Magnetic Means (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)
  • Sampling And Sample Adjustment (AREA)
PCT/JP2004/017603 2004-11-26 2004-11-26 固体核磁気共鳴装置用試料管 WO2006057046A1 (ja)

Priority Applications (5)

Application Number Priority Date Filing Date Title
PCT/JP2004/017603 WO2006057046A1 (ja) 2004-11-26 2004-11-26 固体核磁気共鳴装置用試料管
DE200511002951 DE112005002951T9 (de) 2004-11-26 2005-04-15 Probenröhrchen für Hochgeschwindigkeits-Rotationsverfahren um den magischen Winkel einer Festkörper-Kernresonanzspektroskopie-Vorrichtung und Messverfahren von kernmagnetischen Resonanzspektren unter Verwendung davon
US11/791,543 US7482810B2 (en) 2004-11-26 2005-04-15 Sample tube for solid-state nuclear magnetic resonance apparatus magic angle high-speed rotation method and method for measuring nuclear magnetic resonance absorption spectrum employing it
JP2006546621A JPWO2006057082A1 (ja) 2004-11-26 2005-04-15 固体核磁気共鳴装置マジック角高速回転法用試料管、及び、それを用いた核磁気共鳴吸収スペクトルの測定方法
PCT/JP2005/007303 WO2006057082A1 (ja) 2004-11-26 2005-04-15 固体核磁気共鳴装置マジック角高速回転法用試料管、及び、それを用いた核磁気共鳴吸収スペクトルの測定方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2004/017603 WO2006057046A1 (ja) 2004-11-26 2004-11-26 固体核磁気共鳴装置用試料管

Publications (1)

Publication Number Publication Date
WO2006057046A1 true WO2006057046A1 (ja) 2006-06-01

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2004/017603 WO2006057046A1 (ja) 2004-11-26 2004-11-26 固体核磁気共鳴装置用試料管
PCT/JP2005/007303 WO2006057082A1 (ja) 2004-11-26 2005-04-15 固体核磁気共鳴装置マジック角高速回転法用試料管、及び、それを用いた核磁気共鳴吸収スペクトルの測定方法

Family Applications After (1)

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PCT/JP2005/007303 WO2006057082A1 (ja) 2004-11-26 2005-04-15 固体核磁気共鳴装置マジック角高速回転法用試料管、及び、それを用いた核磁気共鳴吸収スペクトルの測定方法

Country Status (4)

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US (1) US7482810B2 (de)
JP (1) JPWO2006057082A1 (de)
DE (1) DE112005002951T9 (de)
WO (2) WO2006057046A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9494540B2 (en) 2006-08-21 2016-11-15 Aspect Ai Ltd. System and method for a nondestructive on-line testing of samples
CA2672798A1 (en) * 2006-12-08 2008-06-12 Doty Scientific, Inc. Improved nmr cryomas probe for high-field wide-bore magnets
JP2010540929A (ja) * 2007-09-28 2010-12-24 ティツー・バイオシステムズ・インコーポレーテッド プラスチック製サンプル容器を用いるｎｍｒ装置による診断
DE102013217227A1 (de) * 2013-08-29 2015-03-05 Bruker Biospin Gmbh NMR-Spektrometer mit ergonomisch günstigem Probenwechsler
DE202014104679U1 (de) * 2014-09-15 2014-10-08 Aspect Ai Ltd. Eine NMR-extrahierbare Fühlerkassette
US10295487B2 (en) 2014-10-15 2019-05-21 The Curators Of The University Of Missouri In situ NMR parameter monitoring systems and methods for measuring pH and temperature
US10067079B2 (en) * 2014-10-15 2018-09-04 The Curators Of The University Of Missouri Solid state NMR spectroscopy/imaging in situ measuring devices and methods for calibration and determining one or more quantitative properties of a target sample
US10126380B2 (en) 2015-06-15 2018-11-13 Norell, Inc. Closure and system for NMR sample containers with a secondary locking seal

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55101342U (de) * 1979-01-08 1980-07-15
JPS5670547U (de) * 1979-11-02 1981-06-10
JPS5810134Y2 (ja) * 1977-08-30 1983-02-24 日本電子株式会社 電子スピン共鳴装置に用いられる偏平試料管の角度合わせ用治具
JPS5852552A (ja) * 1981-09-24 1983-03-28 Hitachi Ltd Ｆｔ・ｎｍｒ試料回転装置
JPS58167947A (ja) * 1982-03-29 1983-10-04 Hitachi Ltd 核磁気共鳴装置のスピンナ
JPH05249214A (ja) * 1991-12-19 1993-09-28 Varian Assoc Inc Ｎｍｒサンプルシェーパー
US5517856A (en) * 1994-05-11 1996-05-21 Bruker Analytische Messtechnik Gmbh NMR sample holder

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1018186A (en) 1973-10-25 1977-09-27 Serge R. Dolhyj Catalyst compositions especially useful for preparation of unsaturated acids
JPS601715Y2 (ja) * 1979-12-31 1985-01-18 エステ−化学株式会社 芳香消臭液揮散装置
US5469061A (en) * 1993-04-02 1995-11-21 Battelle Memorial Institute Spectrometer capillary vessel and method of making same
US7075303B2 (en) * 2003-07-30 2006-07-11 Syracuse University Polymeric NMR sample tubes and method for using

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5810134Y2 (ja) * 1977-08-30 1983-02-24 日本電子株式会社 電子スピン共鳴装置に用いられる偏平試料管の角度合わせ用治具
JPS55101342U (de) * 1979-01-08 1980-07-15
JPS5670547U (de) * 1979-11-02 1981-06-10
JPS5852552A (ja) * 1981-09-24 1983-03-28 Hitachi Ltd Ｆｔ・ｎｍｒ試料回転装置
JPS58167947A (ja) * 1982-03-29 1983-10-04 Hitachi Ltd 核磁気共鳴装置のスピンナ
JPH05249214A (ja) * 1991-12-19 1993-09-28 Varian Assoc Inc Ｎｍｒサンプルシェーパー
US5517856A (en) * 1994-05-11 1996-05-21 Bruker Analytische Messtechnik Gmbh NMR sample holder

Also Published As

Publication number Publication date
US20080007262A1 (en) 2008-01-10
DE112005002951T9 (de) 2008-03-13
DE112005002951T5 (de) 2007-10-11
US7482810B2 (en) 2009-01-27
WO2006057082A1 (ja) 2006-06-01
JPWO2006057082A1 (ja) 2008-06-05

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